U.S. patent number 5,844,063 [Application Number 08/954,596] was granted by the patent office on 1998-12-01 for resinous copolymer comprising monomer units of each of the groups of phenol compounds and olefinically unsaturated non-acidic terpene compounds.
This patent grant is currently assigned to Arizona Chemical, S.A.. Invention is credited to Jacques Salvetat, Ronald Wind.
United States Patent |
5,844,063 |
Salvetat , et al. |
December 1, 1998 |
**Please see images for:
( Certificate of Correction ) ** |
Resinous copolymer comprising monomer units of each of the groups
of phenol compounds and olefinically unsaturated non-acidic terpene
compounds
Abstract
The present invention relates to a resinous copolymer comprising
monomer units of each of the groups of phenol compounds (I) and
olefinically unsaturated non-acid terpene compounds (II),
characterized in that the copolymer contains monomer units from the
group of polyunsaturated olefin compounds (III), the monomer units
of compound (III) being 1 to 70% by weight of the total of the
monomer units of compounds (II) and (III), the monomer units of
compounds (II) and (III) being at least 50% by weight of the total
of monomer units of compounds (I), (II) and (III). The melting
point of the copolymer is at least 130.degree. C. The copolymers
are particularly useful in printing ink formulations.
Inventors: |
Salvetat; Jacques (Villeneuve,
FR), Wind; Ronald (Emmen, NL) |
Assignee: |
Arizona Chemical, S.A. (Niort,
FR)
|
Family
ID: |
24043158 |
Appl.
No.: |
08/954,596 |
Filed: |
October 20, 1997 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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513413 |
Aug 10, 1993 |
5723566 |
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Current U.S.
Class: |
528/205; 528/106;
525/391; 525/398; 525/480; 525/392; 525/390; 106/31.13;
524/508 |
Current CPC
Class: |
C08G
61/02 (20130101); C08L 65/00 (20130101); C09D
11/106 (20130101); C08L 65/00 (20130101); C08L
2666/18 (20130101); C08L 65/00 (20130101); C08L
61/04 (20130101); C08L 67/08 (20130101); C08L
61/06 (20130101) |
Current International
Class: |
C08L
65/00 (20060101); C09D 11/10 (20060101); C08G
61/02 (20060101); C08G 61/00 (20060101); C08L
61/06 (20060101); C08L 61/00 (20060101); C08L
67/00 (20060101); C08L 67/08 (20060101); C08G
063/78 (); C08L 061/02 (); C09D 011/00 () |
Field of
Search: |
;528/106
;525/390,391,392,398,480 ;186/2R |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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2209779 |
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May 1974 |
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FR |
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1043159 |
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Jun 1963 |
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GB |
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Primary Examiner: Truong; Duc
Attorney, Agent or Firm: Luedeka, Neely & Graham,
P.C.
Parent Case Text
This application is a division of application Ser. No. 08/513,413,
filed Aug. 10, 1995, now U.S. Pat. No. 5,723,566, which is a
continuation of PCT/NL94/00021 filed Jan. 27, 1994.
Claims
We claim:
1. A method for making a resinous copolymer which comprises
reacting, in the presence of a Lewis acid catalyst, a mixture
containing at least one monomer unit from each of the groups of
phenol compounds (I), olefinically unsaturated non-acidic terpene
compounds (II) and aliphatic, non-terpenic polyunsaturated olefin
compounds (III), wherein the monomer units of compound (III)
comprise from about 1 to about 70% by weight of the total weight of
the monomer units of compounds (II) and (III), and wherein monomer
units of compounds (II) and (III) are at least about 50% by weight
of the total weight of the monomer units of compounds (I), (II) and
(III).
2. The method according to claim 1 wherein the monomer units are
reacted by a reverse cationic polymerisation process in the
presence of a solvent.
3. The method according to claim 1 further comprising reacting the
copolymer with at most about 50% by weight (based on the total
copolymer weight) of a formaldehyde, a precondensed phenol
formaldehyde resin or an unsaturated carboxylic acid selected from
the group consisting of unsaturated monocarboxylic acids,
unsaturated dicarboxylic acids and unsaturated carboxylic acid
anhydrides.
4. The method according to claim 3 wherein the carboxylic acid
groups have been wholly or partly esterified with alcohols and/or
have been modified by salt formation.
5. A method for making a printing ink which comprises mixing a
printing ink and a copolymer containing monomer units from of each
of the groups of phenol compound (I), olefinically unsaturated
non-acidic terpene compound (II) and aliphatic, non-terpenic
polyunsaturated olefin compound (III), wherein the monomer units of
compound (III) comprise from about 1 to about 70% by weight of the
total weight of the monomer units of compounds (II) and (III), and
wherein the monomer units of compounds (II) and (III) are at least
about 50% by weight of the total weight of the monomer units of
compounds (I), (II) and (III).
6. The method of claim 5, wherein the amount of the monomer units
of compound (III) comprises from about 5 to about 50% by weight of
the total weight of monomer units of compounds (II) and (III).
7. The method of claim 5 wherein the copolymer contains from about
10 to about 40% by weight of monomer units of compound (I), from
about 30 to about 80% by weight of monomer units of compound (II)
and from about 5 to about 30% by weight of monomer units of
compound (III), based on the total weight of the monomer units of
compounds (I), (II) and (III).
8. The method of claim 5 wherein the monomer units of compound (II)
comprise at least about 80% by weight cyclic olefinically
unsaturated non-acidic terpene compounds.
9. The method of claim 8, wherein the cyclic terpene compound is
alpha-pinene.
10. The method of claim 5 wherein the monomer units of compound
(III) comprise at least about 80% by weight cyclic polyunsaturated
olefin units.
11. The method according to claim 10, wherein the cyclic
polyunsaturated olefin compound is dicyclopentadiene.
12. The method of claim 5 wherein the copolymer contains at most
about 15% by weight vinyl aromatic monomer.
13. Printing ink comprising ink and a resinous copolymer made by
the process according to claim 1.
14. The method according to claim 2 further comprising reacting the
copolymer with at most about 50% by weight (based on the total
copolymer weight) of a formaldehyde, a precondensed phenol
formaldehyde resin or an unsaturated carboxylic acid selected from
the group consisting of unsaturated monocarboxylic acids,
unsaturated dicarboxylic acids and unsaturated carboxylic acid
anhydrides.
15. The method according to claim 14 wherein the carboxylic acid
groups have been wholly or partly esterified with alcohols and/or
have been modified by salt formation.
16. The method of claim 6 wherein the copolymer contains from about
10 to about 40% by weight of monomer units of compound (I), from
about 30 to about 80% by weight of monomer units of compound (II)
and from about 5 to about 30% by weight of monomer units of
compound (III), based on the total weight of the monomer units of
compounds (I), (II) and (III).
17. The method of claim 6 wherein the monomer units of compound
(II) comprise at least about 80% by weight cyclic olefinically
unsaturated non-acidic terpene compounds.
18. The method of claim 6 wherein the monomer units of compound
(III) comprise at least about 80% by weight cyclic polyunsaturated
olefin units.
19. The method of claim 6 wherein the copolymer contains at most
about 15% by weight vinyl aromatic monomer.
20. Printing ink comprising ink and a modified copolymer made
according to claim 3.
Description
The invention relates to a resinous copolymer comprising monomer
units of each of the groups of phenol compounds (I) and
olefinically unsaturated non-acidic terpene compounds (II).
Such resinous copolymers (so-called terpenephenolic resins) are
disclosed in SU-A-1073249. A drawback of said terpene-phenolic
resins is their relatively low melting point of at most 120.degree.
C. Consequently these terpene-phenolic resins are not suitable for
use in printing inks applications, for which a higher melting
point, particularly for rapid drying of the ink, is desirable. A
further drawback is their relatively insensitivety to modification
reactions. In printing ink applications modifiability is desirable
for adapting certain properties of the resinous copolymer to the
desired properties of the printing ink such as, for example, the
viscosity, the solubility and the pigment-wetting properties.
The object of the invention is to provide a resinous copolymer
comprising monomer units of each of the groups of phenol compounds
(I) and olefinically unsaturated non-acidic terpene compounds (II)
for use in printing inks.
This copolymer according to the invention is characterized in that
the copolymer also contains monomer units from the group of
polyunsaturated olefin compounds (III), the monomer units of
compound (III) being 1 to 70% by weight of the total of the monomer
units of compounds (II) and (III), and the monomer units of
compounds (II) and (III) being at least 50% by weight of the total
of the monomer units of compound (I), (II) and (III).
Preferably the melting point of the copolymer is at least
130.degree. C.
More preferably, the melting point is at least 140.degree. C.
The term "melting point" refers to the "ring and ball" softening
point (according to ASTM E28).
The Japanese patent application 47035000 discloses that resinous
copolymers consisting of monomer units of compounds (I) and (III)
have a much lower melting point than the above-mentioned
terpene-phenolic resins consisting of monomer units of compounds
(I) and (II). Surprisingly, the presence of the monomer units of
compound (III) in addition to monomer units of compounds (I) and
(II) results in a higher melting point of the resinous
copolymer.
A further advantage of the resinous copolymers according to the
invention is that now use can be made of terpene compound (II)
which would result in a relatively low melting point when used in
the corresponding terpene-phenolic resin for this application.
Terpene compounds resulting in resins having a relatively low
melting point are generally more readily available and cheaper.
Another advantage of the resinous copolymer according to the
invention is the very good modifiability.
The resinous copolymers according to the invention further have
also a very good solubility in aromatic-free mineral oils and good
wetting behaviour towards pigments. The resinous copolymers are
also very stable towards oxydation which does not decrease the
solubility in mineral oils. Furthermore they show good drying
properties. As a result of these properties, the resinous
copolymers are in particular very suitable for use in printing
inks.
If the amount of the monomer units of compound (III) is 5 to 50% by
weight of the monomer units of compounds (II) and (III) higher
melting points and better solubility in aromatic-free mineral oils,
can be obtained.
Preferably, the resinous copolymer according to the invention
contains 5-50% by weight of monomer units of compound (I), 15-80%
by weight of monomer units of compound (II) and 0.5-50% by weight
of monomer units of compound (III), based on the total weight of
the monomer units of compounds (I), (II) and (III).
More preferably the resinous copolymer according to the invention
contains 10-40% by weight of monomer units of compound (I), 30-80%
by weight of monomer units compound (II) and 5-30% by weight of
monomer units of compound (III), based on the total weight of the
monomer units of compounds (I), (II) and (III).
A content of more than 10% by weight of monomer units of compound
(I) results in good pigment wetting and a good start of the
polymerization reaction. If the content is more than 40% by weight,
lower melting points and lower solubility in aromatic-free solvents
are achieved. A content of at least 30% by weight of monomer units
of compound (II) is important for a high melting point, a good
solubility, even in aromatic-free solvents, and a high drying
rate.
More preferably, the content of monomer units of compound (II) is
at least 40% by weight.
Preferably, the resinous copolymer has at least 5% by weight of
monomer units of compounds (III), in order to achieve a higher
melting point and good modifiability. More preferably, said content
is at least 10% by weight. A resinous copolymer with a monomer
compound (III) content in excess of 30% has lower solubility in
aromatic-free mineral oils.
Suitable phenol compounds (I) include mono- or polyhydric, mono- or
polynuclear, substituted or unsubstituted phenol compounds such as
for example phenol, mono-, di- or trialkyl- or alkoxyphenols, the
alkyl or alkoxy groups having 1-12 carbon atoms, chlorinated
phenols, thiophenols or mixtures of said phenol compounds.
Preferably, the phenol compound (I) is phenol or an alkylphenol
having 1-12 carbon atoms. Preferably the alkylphenol is butyl-,
octyl- or nonylphenol.
Preferably, the olefinically unsaturated non-acidic terpene
compound (II) comprises 5 to 40, and more preferably 5 to 20,
carbon atoms.
The monomer units of compound (II) may be pure substances or
mixtures of various olefinically unsaturated non-acidic terpene
compounds.
Preferably the monomer units of compound (II) have a high content
of cyclic olefinically unsaturated non-acidic terpene compounds.
The monomer units of compound (II) in the resinous copolymer
preferably comprise at least 80% by weight, and more preferably at
least 90% by weight, of cyclic olefinically unsaturated non-acidic
terpene compounds.
Suitable olefinically unsaturated non-acidic terpene compounds, as
the pure monomer units of compound (II) or as a component in a
mixture of monomer units of compounds (II) include alpha-pinene,
beta-pinene, sabinene, limonene, carene and dipentene. Preferably
compound (II) is alpha-pinene.
The mixtures used in practice may be industrial grades or
concentrates which mainly comprise monomer units of compound (II).
Said mixtures may be distillates or extracts of natural raw
materials such as, for example, of natural resins. Good results can
be achieved with turpentines which are mixtures of alpha- and
beta-pinene and other terpenes. Preferably, turpentines having a
high alpha-pinene content are used.
Preferably, the polyunsaturated olefin compounds (III) have 4-20
carbon atoms. They must have one or more cationically polymerizable
unsaturated bonds and one or more unsaturated bonds which can be
reacted non-cationically under the conditions of the polymerization
reaction. As a result, the resinous copolymer is partially
unsaturated after the reaction of the monomer units of compounds
(I), (II) and (III).
Suitable polyunsaturated olefin compounds include, cycloaliphatic
dienes or trienes such as, for example, dicyclopentadiene (DCPD),
cyclopentadiene, cyclooctadiene or cyclohexadiene or non-cyclic
aliphatic dienes or trienes, whose double bonds are preferably
conjugated, such as, inter alia, butadiene, piperylene or
1,3-octadiene. Preferably, doubly unsaturated olefin compounds are
used.
The polyunsaturated olefin compound (III) may be a pure substance
or a mixture of various monomer compounds (III).
Suitable high melting points, can be achieved if in the resinous
copolymer the monomer compound (III) comprise at least 60% by
weight, more preferably at least 80% by weight, of cyclic
polyunsaturated olefin compounds. Preferably the cyclic
polyunsaturated olefin compound is dicyclopentadiene.
Good results are achieved in particular if at least 80% by weight,
or more preferably at least 90% by weight, of both the non-acidic
terpene compound (II) and the polyunsaturated olefin compound (III)
are cyclic compounds. Preferably, said compounds are alpha-pinene
and dicyclopentadiene.
The resinous copolymer can be prepared by cationic polymerization,
using a Lewis acid catalyst. Suitable catalysts include for example
BF.sub.3, BCl.sub.3 and complexes of BF.sub.3 with, for example,
water, alkyl alcohols, phenols or ethers. Preferably BF.sub.3 is
used.
The resinous copolymer according to the invention can also be
prepared by other methods.
For example, the monomer compounds can first be blended together,
after which the catalyst is added in small amounts with stirring.
This method is particularly suitable if relatively small amounts of
phenol compound (I) have to be incorporated.
Preferably the resinous copolymer is prepared according to a
"reverse" cationic polymerization in a solvent. "Reverse" means
that, in contrast to the method described above, an activated
complex is first formed between the catalyst and the phenol
compounds (I), after which the remaining monomer units are added.
This method makes it possible to incorporate higher proportions of
phenol compounds. Both methods can be applied with or without a
solvent. By using a solvent, the reaction can proceed at lower
temperatures.
The solvent may be an alkylatable solvent or a solvent which is
inert with regard to the polymerization reaction.
An alkylatable solvent consists wholly or partially of aromatic
substances which may be incorporated in small amounts into the
resinous copolymer during the polymerization reaction. Suitable
alkylatable solvents include toluene, xylene, trimethylbenzene
(which compounds may or may not be substituted by aliphatic
molecules) and mixtures of such compounds with a compound which is
inert with regard to the polymerization reaction. An advantage of
these aromatic groups containing solvents is the better solubility
of the reactants and the reaction products, as a result of which a
more homogeneous reaction mixture is obtained. The aromatic
alkylating compounds from the solvent which are incorporated in the
resinous copolymer have a positive influence on the solubility of
the resinous copolymer in aromatic-containing solvents.
Preferably, the solvent is a compound, or a mixture of compounds
being inert with regard to the polymerization reaction. Especially
in conjunction with a low reaction temperature, they result in very
high melting points and in products which are readily soluble in
substantially aromatic-free mineral solvents.
Suitable inert solvents include aliphatic compounds which may be
chlorinated. Preferably, the solvent is an alkane and more
preferably an alkane having 5 to 10 carbon atoms, such as for
example heptane. In many cases, in particular at a low reaction
temperature, it is preferred to combine the advantages of both the
alkylating solvents and the inert compounds by using a mixture of
them.
A further advantage of a "reverse" cationic polymerization in an
inert solvent is that the copolymer composition is substantially
completely stoichiometrically defined by the choice of the
proportions of the monomers employed.
The reaction temperature is preferably below 60.degree. C. and more
preferably below 40.degree. C. At these temperatures alkylating
solvents can be used, even if good solubility in aromatic-free
solvents is required. At low reaction temperatures only small
amounts of the alkylatable compounds from the solvents are
incorporated in the resinous copolymer.
In addition to the monomers (I), (II) and (III), the resinous
copolymers according to the invention optionally may also contain
minor amounts, preferably 0.5-30% by weight, more preferably
0.5-15% by weight, and most preferably 0.5-5% by weight, of other
non-acidic copolymerizable monomers, such as, for example, vinyl
aromatics or alkenes. Said monomers may be added before, during or
after the polymerization reaction of the monomers (I), (II) and
(III).
For use in printing inks the amount of vinyl aromatic units is
preferably less than 15% by weight, preferably less than 10% by
weight, and more preferably less than 5% by weight. These amount
results in a good solubility of the resin in the ink and effective
drying of the ink.
After the polymerization reaction and neutralization of the
catalyst, the resinous copolymer is isolated from the reaction
product and purified, by generally known methods.
Generally the weight average molecular weight (Mw) of the base
resin is at most 1500.
By modification of the base resin with other compounds it is
possible to adjust particular properties of the resinous copolymer
to the requirements of particular applications.
The resinous copolymer comprising monomer units of compounds (I),
(II) and (III) can be modified with at most 50% by weight, and more
preferably at most 30% by weight (based on the total copolymer
weight), of other compounds. The modification can take place before
or after the above-mentioned reaction product is upgraded to yield
the resinous copolymer.
The resinous copolymer can be modified with, for example an
unsaturated carboxylic acid, such as for example unsaturated
monocarboxylic acids, unsaturated dicarboxylic acids or unsaturated
carboxylic acid anhydrides. Preferably, carboxylic acid anhydride
and in particular maleic anhydride are used.
In another preferred embodiment of the invention the carboxylic
acid groups of the above-mentioned modified resinous copolymer have
been also wholly or partially esterified with alcohols, and/or have
been modified by salt formation.
In yet another embodiment of the invention the resinous copolymer,
which may or may not have been modified in the above-mentioned way,
is further modified by condensation with formaldehyde or with a
precondensed phenol-formaldehyde resin.
The weight-average molecular weight also increases concomitantly.
The weight-average molecular weight is measured by means of Gel
Permeation Chromatography (GPC) according to the SAM-5019
method.
The resinous copolymer according to the invention having a melting
point of at least 130.degree. C. also includes said modified
copolymers having a melting point of at least 130.degree. C.
The resinous copolymer according to the invention consists of a
skeleton of non-acidic monomer units of compounds (I), (II), (III),
which have been linked together in one polymerization step, and
optionally a minor amount of copolymerizable non-acidic monomer
compounds to which, in a second reaction step, other compounds such
as, in particular, acidic monomer compounds are reacted.
The resinous copolymers according to the invention are excellently
suitable for use in printing inks. Resinous copolymers according to
the invention have a high melting point, good wetting behaviour
with regard to pigments, good solubility even in aromatic-free
solvents, good oxidation resistance and a high drying rate.
The solubility of the resinous copolymers can be expressed by the
cloud point. The cloud point is the maximum temperature at which,
at a certain content, the resinous copolymer is still just soluble
in a solvent. A low cloud point corresponds to good solubility. The
base resin preferably has a cloud point, at a content of 10% by
weight in an aromatic-free mineral oil (Haltermann PKWF 6/9 AF), of
at most 100.degree. C., and more preferably of at most 75.degree.
C. The cloud point measurements are carried out using a DSM
Chemotronic cloud point meter (10% by weight of a solution of the
resinous copolymer being heated to 230.degree. C. and then
gradually being cooled down. At the temperature at which the resin
is just no longer soluble, the solution becomes cloudy and the
trajectory of an IR beam is interrupted thereby).
U.S. Pat. No. 3,383,362 discloses phenol-terpene-cyclic polyolefin
polymers having softening points below 123.degree. C. These
polymers are for use in ethylene-propylene rubber adhesives. This
patent does not give any suggestion to use the polymers in printing
ink applications.
GB-B-1043159 discloses terpene phenolic resins having melting
points below 109.degree. C. for use as antioxidizing agents for oil
of turpentine and, moreover, they are valuable intermediate
products. This specification does not give any suggestion to use
the resins in printing ink applications.
U.S. Pat. No. 4,105,610 discloses resinous copolymers containing
monomer units from the groups (I) and (II) U.S. Pat. No. 4,105,610
describes a reaction product of a diolefin polymer having a phenol
and an olefinically unsaturated carboxylic acid, in which the
diolefin polymer may, inter alia, be a copolymer of polyunsaturated
diolefins with a minor quantity of a copolymerizable monomer, which
monomer may, apart from a large number of other compounds,
optionally also be a non-acidic terpene compound. These copolymers
have a lower melting point at a comparable molecular weight. U.S.
Pat. No. 4,105,610 does not teach that the resinous copolymers
according to the present invention, having a relatively high
content of non-acidic terpene compounds, will have said high
melting points.
EP-A-210706 and EP-A-209956 describe resinous copolymers for use in
adhesives and coatings, which largely consist of vinyl aromatic
monomer with a minor amount of other copolymerizable monomers,
selected from a large group which, inter alia, comprises monomer
compounds (I), (II) or (III). Said resinous copolymers have low
solubility in aromatic-free mineral oils and dry poorly. A further
important drawback of the resinous copolymers according to
EP-A-209956 is that they cannot be modified. EP-A-210706 and
EP-A-209956 do not provide resinous copolymers having a relatively
high melting point.
The invention will hereinafter be explained in more detail by the
following non-restrictive examples.
EXAMPLE I
In a double-walled, cooled 1.5 l reactor equipped with stirrer,
reflux condenser, thermocouple and gas inlet tube, 520 g of toluene
and 200 g of phenol were successively combined. The solution was
heated to 35.degree. C., the phenol being dissolved during
stirring. After all phenol had dissolved, BF.sub.3 gas was fed at a
rate of 40 ml a minute, so that a BF.sub.3 -phenol complex was
formed. After the phenol solution was saturated with BF.sub.3
(approx. 2500 ml=7.5 g of BF.sub.3), the BF.sub.3 feed was
stopped.
Subsequently, a monomer mixture of 444 g of .alpha.-pinene (>95%
pure) and 137.2 g of dicyclopentadiene (95% pure) was fed to the
complex formed, the feeding rate being such that the average
polymerization temperature was 35.degree. C. After addition of the
entire monomer mixture, stirring took place for 60 minutes at
35.degree. C. The BF.sub.3 was neutralized through addition of 26 g
of Ca(OH).sub.2 at 90.degree. C. After filtration, the resin was
freed of solvent, oligomers and non-converted monomers by means of
vacuum distillation and passing through of nitrogen.
In this way 663 g of resin having the following properties was
obtained:
R&B melting point=146.degree. C.,
Mw (with regard to polystyrene)=1100,
Mn (with regard to polystyrene)=680,
cloud point (10%) in aromatic-free mineral oil (Haltermann PKWF
6/9AF)=60.degree. C.
viscosity (50%) in aliphatic mineral oil (Halterman PKWF 6/9 AFN)
at 23.degree. C.=44 dPas.
EXAMPLE II
Example I was repeated with a different monomer mixture. In this
example a monomer mixture of 238 g of .alpha.-pinene (>95% pure)
and 297 g of dicyclopentadiene (95% pure) was added to the BF.sub.3
-phenol complex.
In this way 702 g of resin having the following properties was
obtained:
R&B melting point=148.degree. C.,
Mw (with regard to polystyrene)=1135,
Mn (with regard to polystyrene)=620,
cloud point (10%) in aromatic-free mineral oil (Haltermann PKWF
6/9AF)=84.degree. C.
Comparison of Examples I and II shows that the solubility in
aromatic-free mineral oil decreases when the content of monomer
units (III) exceeds 30%.
Comparative experiment A
Example I was repeated with a different monomer mixture. In this
example 574 g of dicyclopentadiene was added to the BF.sub.3
-phenol complex.
In this way a resin having the following properties was
obtained:
R&B melting point <20.degree. C.,
Mw (with regard to polystyrene)=280,
Mn (with regard to polystyrene)=210,
cloud point (10%) in aromatic-free mineral oil (Haltermann PKWF
6/9AF)=<20.degree. C.
Comparative Experiment A shows that a resinous copolymer consisting
of monomer units (I) and (III) has a very low melting point.
Comparative experiment B
Example I was repeated with a different composition of the monomer
mixture. In this example 581 g of .alpha.-pinene (>95% pure) was
added to the BF.sub.3 -phenol complex.
In this way a resin having the following properties was
obtained:
R&B melting point=110.degree. C.,
Mw (with regard to polystyrene)=800,
Mn (with regard to polystyrene)=590,
cloud point (10%) in aromatic-free mineral oil (Haltermann PKWF
6/9AF)=41.degree. C.
Comparative experiment B shows that a resinous copolymer consisting
of monomer units (I) and (II) has a lower melting point than the
resinous copolymer according to Example I.
Comparative experiment C
Example I was repeated with a different composition of the monomer
mixture. In this example a monomer mixture of 683.1 g of C.sub.9
cracker fraction (60-65% cationically polymerizable) and 137.2 g of
dicyclopentadiene (95% pure) was added to the BF.sub.3 -phenol
complex.
The C.sub.9 cracker fraction substantially consists of aromatic
compounds such as for example indene, vinyl toluene, styrene and
.alpha.-methylstyrene.
In this way 724 g of resin having the following properties was
obtained:
R&B melting point=59.degree. C.,
Mw (with regard to polystyrene)=590,
Mn (with regard to polystyrene)=400,
cloud point (10%) in aromatic-free mineral oil (Haltermann PKWF
6/9AF)=89.degree. C.
Comparative experiment C shows that when use is made of a C.sub.9
fraction in place of the monomer units (II) a very low melting
point and low solubility are obtained (in comparison with the
resinous copolymer according to Example I).
EXAMPLE III
Example I was repeated with a different composition of the monomer
mixture. In this example a monomer mixture of 365.9 g of
.alpha.-pinene (>95% pure), 78.1 g of paramethylstyrene (99%
pure) and 137.2 g of dicyclopentadiene (95% pure) was added to the
BF.sub.3 -phenol complex.
In this way 668 g of a resin having the following properties was
obtained:
R&B melting point=145.degree. C.,
Mw (with regard to polystyrene)=1110,
Mn (with regard to polystyrene)=700,
cloud point (10%) in aromatic-free mineral oil (Haltermann PKWF
6/9AF)=67.degree. C.
Example III shows that (compared to Comp. experiment C) a higher
melting point as well as better solubility can be achieved if the
content of vinyl aromatic compounds (78.1 g paramethylene instead
of 683,1 g C9-cracker/fraction) is relatively low.
EXAMPLE IV
Example I was repeated with methylcyclohexane as solvent.
In this way 616 g of resin having the following properties was
obtained:
R&B melting point=158.degree. C.,
Mw (with regard to polystyrene)=1320,
Mn (with regard to polystyrene)=760,
cloud point (10%) in aromatic-free mineral oil (Haltermann PKWF
6/9AF)=47.degree. C.
Example IV shows that both a higher melting point and better
solubility are obtained when use is made of a solvent being inert
with regard to the polymerization reaction.
EXAMPLE V
Example I was repeated with a mixture of 80 parts by weight of
heptane and 20 parts by weight of toluene as solvent.
In this way 638 g of a resin having the following properties was
obtained:
R&B melting point=173.degree. C.,
Mw (with regard to polystyrene)=1430,
Mn (with regard to polystyrene)=820,
cloud point (10%) in aromatic-free mineral oil (Haltermann PKWF
6/9AF)=52.degree. C.
Example V shows that higher melting points can be obtained in
combination with a very small decrease in solubility when use is
made of a mixture of an inert and an alkylating mixture as
solvent.
EXAMPLE VI
Example I was repeated at a polymerization temperature of
60.degree. C.
In this way 649 g of a resin having the following properties was
obtained:
R&B melting point=140.degree. C.,
Mw (with regard to polystyrene)=1320,
Mn (with regard to polystyrene)=650,
cloud point (10%) in aromatic-free mineral oil (Haltermann PKWF
6/9AF)=124.degree. C.
Example VI shows that a higher reaction temperature in an
alkylating solvent (toluene) results in a decrease in
solubility.
EXAMPLE VII
In a 2 l reactor equipped with stirrer, reflux condenser,
thermocouple, inert gas inlet tube and heating jacket, 400 g of the
resin from Example I were melted and heated to 220.degree. C. under
nitrogen. Subsequently, 56 g of a nonyl phenol formaldehyde adduct
were added in 1 hour. The reaction mixture was then stirred for
another hour. Next non-reacted materials were removed by means of
vacuum distillation while nitrogen was being passed through.
In this way a resin having the following properties was
obtained:
R&B melting point=176.degree. C.,
Mw (with regard to polystyrene)=3750,
Mn (with regard to polystyrene)=1030,
cloud point (10%) in aromatic-free mineral oil (Haltermann PKWF
6/9AF)=63.degree. C.,
viscosity (50%) in aliphatic mineral oil (Haltermann PKWF 6/9AFN)
at 23.degree. C.=610 dpa.s.
Example VII shows that modification of the resinous copolymer of
Example I results in, inter alia, a higher melting point and a
strong increase in viscosity.
EXAMPLE VIII
In the reactor described in Example VII, 400 g of the resin from
Example I were melted and heated to 200.degree. C. Subsequently, 10
g of maleic anhydride were added, followed by stirring for 2 hours
at 200.degree. C. Then, successively, 40 g of epoxidized linseed
oil were added, heated to 230.degree. C. and in one hour 80 g of a
nonylphenol-formaldehyde adduct were added. This was followed by
stirring for 1 hour. The non-reacted components were removed by
means of vacuum distillation while nitrogen was being passed
through.
In this way a resin having the following properties was
obtained:
R&B melting point=186.degree. C.,
Mw (with regard to polystyrene)=47100,
Mn (with regard to polystyrene)=1300,
cloud point (10%) in aromatic-free mineral oil (Haltermann PKWF
6/9AF)=164.degree. C.,
viscosity (45%) in aliphatic mineral oil (Haltermann PKWF 28/31AR)
at 23.degree. C.=1300 dpa.s.
EXAMPLE IX
In the reactor described in Example VII, 400 g of the resin from
Example I with 100 g of xylene were heated to 145.degree. C. After
all resin had dissolved, 20 g of maleic anhydride were added,
followed by stirring for 5 minutes. In 30 minutes a 50% solution of
di-tertiary butyl peroxide in xylene was added, which was followed
by stirring for 120 minutes. The temperature was raised to
200.degree. C., followed by stirring for 120 minutes. The
non-reacted components were removed by means of vacuum distillation
while nitrogen was being passed through.
In this way a resin having the following
properties was obtained:
R&B melting point=168.degree. C.,
acid number=13 mg KOH/g resin.
EXAMPLE X
In the reactor described in Example VII, 670 g of the resin from
Example I were dissolved at 145.degree. C. in 75 g of xylene.
Subsequently 213 g of rosin, 50 g of tall-oil fatty acid and 4 g of
zinc oxide were added. The solution was cooled down to 100.degree.
C. At 100.degree. C. 41.1 g of para-formaldehyde were added and the
reaction temperature was raised to 125.degree. C. in 10 minutes.
After stirring for 2 hours at 125.degree. C., the reaction
temperature was raised to 230.degree. C. in 3 hours. At 230.degree.
C. 0.9 g of magnesium oxide were added, followed by stirring for 4
hours. The unreacted components were removed by means of vacuum
distillation while nitrogen was being passed through.
In this way a resin having the following properties was
obtained:
R&B melting point=196.degree. C.,
viscosity in toluene at 23.degree. C.=5.5 dpa.s.
* * * * *